Pre-treatment of sludge

ABSTRACT

A method for treating a sludge to be fed to a bioreactor for treating wastewater, or an anaerobic or aerobic sludge digester, the method comprising contacting the sludge with free nitrous acid.

This application is the U.S. national phase of International ApplicationNo. PCT/AU2012/000725 filed 22 Jun. 2012 which designated the U.S. andclaims priority to AU Patent Application No. 2011902595 filed 30 Jun.2011, the entire contents of each of which are hereby incorporated byreference.

The present invention relates to a process for the pre-treatment ofsludge. In some embodiments, the present invention relates to thepre-treatment of a sludge from a bioreactor for treatingwastewater/secondary treatment in a wastewater treatment plant, with thetreated sludge being fed to an anaerobic digester, an aerobic digesteror back to bioreactor for treating wastewater.

BACKGROUND TO THE INVENTION

Microbial processes play a central role in wastewater management. Inparticular, they underpin biological treatment of wastewater, the mostcost-effective and environmentally friendly method for wastewatertreatment.

A typical advanced wastewater treatment plant receives wastewater fromsewage mains. The wastewater is first treated to remove largeparticulates (by screening, or passing through a primary settler, orboth). The liquor then passes to bioreactors, where bacteria mineraliseorganic carbon (often referred to as biological oxygen demand or BOD) toCO2 and convert ammonia to nitrate, and in some cases further tonitrogen gas. Some bioreactors also achieve biological phosphorusremoval. This process results in the growth of biomass. The biomass isthen separated from the liquor, typically in a secondary settler.

The sludge from the secondary settler (which includes most of theseparated biomass) is then treated in an anaerobic digester or anaerobic digester, sometimes together with primary sludge resulting fromthe settling process in the primary settler. In the anaerobic digester,the BOD of the sludge is converted to methane. Products from theanaerobic digester also include solids that may be disposed of and aliquid stream. In the aerobic digester, part of the organics in thesludge is mineralised thus achieving the stabilisation and a reductionof the sludge to be disposed of.

Variations around this general process described above also exist.

Bioreactors used for treating primary effluent can consist of aerobic,anoxic and even anaerobic zones/conditions. Throughout thisspecification, the term “bioreactor for treating wastewater” is used torefer to any reactor in which microorganisms utilise or catalyseconversion of wastewater stream components into other components. Thebioreactor may be an aerobic bioreactor, an anaerobic bioreactor or ananoxic bioreactor, or it may be operated under two or more suchconditions (typically in sequence, but different zones of a bioreactormay operate under different conditions, for example, a top part of abioreactor may be operating under aerobic conditions and a bottom partof the bioreactor may be operating under anaerobic conditions.

In a typical wastewater treatment plant, both biological nutrientremoval and energy recovery require organic carbon. The requirement forhigh-level nutrient removal from wastewaters has often seen theabolishment of the primary settler, to satisfy the carbon demand fornutrient removal in the downstream processes of the wastewater treatmentplant. However, abolishing the primary settler eliminates an energy richstream for anaerobic digestion. This reduces the energy yield of theplant and renders energy recovery through anaerobic digestioneconomically infeasible for small to medium-sized wastewater treatmentplants.

One reason for the high demand of organic carbon feed for nutrientremoval is biomass production. In this regard, in the bioreactor fortreating wastewater, the reactions that are taking place are typicallybiologically driven. As a result, the microorganisms that catalyse thesereactions grow and a substantial biomass is produced. Thesemicroorganisms assimilate a large amount organic carbon as biomass.Typically, 30 to 40% of the organic carbon fed to the bioreactor isassimilated by bacterial cells in the form of active bacterial cells anddebris resulting from cell death and lysis, and is subsequently removedfrom the bioreactor as excess secondary sludge.

The secondary sludge is often supplied to an anaerobic digester in orderto convert the BOD of the sludge to biogas containing methane. However,this large stream of secondary sludge, although containing large amountsof organic carbon, is poorly biodegradable. Pre-treatment of the sludgeis required to break up bacterial cell walls to make its carbon moreavailable for the reactions in the anaerobic digester, such as methaneproduction, or in another bioreactor for treating wastewater as anexternal carbon source for denitrification.

Various methods have been developed to improve the bioavailability ofthis sludge stream. However, these methods are either energy intensive(such as thermal treatment, sonication, or ozonation) or consume largeamounts of imported chemicals, such as acid, alkali or hydrogenperoxide. This incurs significant economic and environmental costs.

BRIEF DESCRIPTION OF THE INVENTION

In a first aspect, the present invention provides a method for treatinga sludge to be fed to a bioreactor for treating wastewater or ananaerobic or an aerobic sludge digester, the method comprisingcontacting the sludge with free nitrous acid.

In a second aspect, the present invention provides a method for treatinga sludge to be fed to a bioreactor for treating wastewater or ananaerobic or an aerobic sludge digester, the method comprisingcontacting the sludge with nitrite in solution at a pH of less than 7.

In one embodiment, the sludge comprises a sludge from a secondarysettler. Such a sludge may comprise, for example, a sludge removed froma bioreactor for treating wastewater.

In another embodiment, the sludge may comprise a sludge removed from aprimary settler. In a further embodiment, the sludge may comprise amixture of a sludge removed from a bioreactor for treating wastewaterand a sludge removed from a primary settler.

In some embodiments, the treated sludge is used as a feed to ananaerobic or an aerobic digester. In other embodiments, the treatedsludge is used as a feed to a bioreactor for treating wastewater.

In some embodiments, the mixture of sludge and free nitrous acid (thatis formed by contacting the sludge with the free nitrous acid) may havea pH that is less than 6.5, more desirably less than 6.0, even moredesirably less than 4, or even less than 2. A mixture of sludge and freenitrous acid may have a free nitrous acid content of at least 0.05 ppm,preferably at least 0.1 ppm, preferably at least 0.5 ppm, preferably atleast 1 ppm, more suitably at least 2 ppm.

The free nitrous acid may be continuously added to the sludge beingtreated. In other embodiments, the free nitrous acid may be added to thesludge on an intermittent basis.

In some embodiments, the sludge is contacted with free nitrous acid bycontacting the sludge with a liquid stream containing free nitrous acid,such as an aqueous stream containing free nitrous acid.

The liquid stream containing free nitrous acid or containing nitrite mayhave a pH that is less than 6.5, more desirably less than 6.0. In someembodiments, the pH of the liquid stream containing free nitrous acidmay be less than 4, or even less than 2. The liquid stream may comprisea liquid stream containing nitrite and having an acidic pH. It will beappreciated that free nitrous acid is formed when liquid streamscontaining nitrite have an acidic pH. Generally, a lower pH value for aliquid stream containing nitrite will result in a higher content of freenitrous acid.

In some embodiments, the liquid stream containing free nitrous acid hasa free nitrous acid content of at least 0.5 ppm, preferably at least 1ppm, more suitably at least 2 ppm.

The liquid stream containing free nitrous acid may be continuously addedto the sludge being treated. In other embodiments, the liquid streamcontaining free nitrous acid may be added to the sludge on anintermittent basis.

The sludge and the liquid containing free nitrous acid may be contactedtogether using any suitable contacting apparatus. For example, thesludge and the liquid containing free nitrous acid may be mixed in astirred tank or in an agitated tank. Any type of agitation known to besuitable to the person skilled in the art, such as stirrers, paddles ordraft tubes, may be used.

According to a third aspect, the present invention provides a method fortreating a sludge comprising treating the sludge in accordance with thefirst aspect of the present invention or the second aspect of thepresent invention and passing the treated sludge to a digester or to abioreactor for treating wastewater.

The present inventors have found that adding free nitrous acid to thesludge acts to kill much of the bacteria and microorganisms in thesludge. This enhances the biodegradability of the sludge and thereforemakes more of the sludge available to the microorganisms in thebioreactor for treating wastewater or in the anaerobic or an aerobicsludge digester. Accordingly, the quality of “feed” for themicroorganisms in the bioreactor for treating wastewater or in theanaerobic or an aerobic sludge digester that receives the treated sludgeis improved. The present inventors also believe that adding free nitrousacid to the sludge causes lysis of the cell membranes of microorganismsin the sludge. This also assists in improving the biodegradability ofthe sludge.

The sludge may be treated by contacting it with the liquid containingfree nitrous acid and subsequently the treated sludge may be fed to abioreactor for treating wastewater or to an anaerobic or an aerobicsludge digester. Alternatively, the sludge may undergo further treatmentusing conventional treatment steps prior to being fed to the bioreactoror digester. The conventional treatment steps may take place aftertreatment of the sludge with free nitrous acid, at the same time astreatment of the sludge with free nitrous acid or before treatment ofthe sludge with free nitrous acid.

The present inventors believe that the amount of free nitrous acid addedper kilogram of sludge is unlikely to be especially critical. Once aminimum concentration of free nitrous acid is achieved or maintained,the present inventors believe that the advantageous effects of thepresent invention should be achieved. It is possible that for thickersludges, the more difficult it may be for the free nitrous acid todiffuse into flocs. Therefore, for thicker sludges, the concentration offree nitrous acid in the liquid phase may need to be higher to beeffective. Further, as the free nitrous acid is generated by providing anitrite containing solution having an acidic pH, some levels of nitriteconsumption may take place during treatment and a higher biomassconcentration may lead to a higher rate of consumption of nitrite.However, experimental work conducted by the inventors to date hasobserved little nitrite consumption.

In some embodiments of the present invention, the treatment of thesludge can be controlled such that nitrogen removal with the sludge canoccur via the nitrite pathway, that is, through ammonium oxidation tonitrite and then nitrite reduction to dinitrogen gas. This pathway canbe schematically described as NH4+□NO2-□N2. In particular, the operatingpremise of the method can be controlled such that nitrite oxidisingbacteria are largely eliminated from the system whilst ammoniumoxidising bacteria remained in the system. In some embodiments, theconcentration of free nitrous acid, the duration of treatment with freenitrous acid and the solids retention time can be controlled such thatnitrite oxidising bacteria are largely eliminated from the system whilstammonium oxidising bacteria remained in the system. This process canreduce the oxygen requirement for nitrification by up to 25% and thecarbon requirement for denitrification by up to 40%.

This embodiment of the present invention is based upon the discoverythat treatment with FNA results in the reduction of ammonium oxidisingbacteria (AOB), nitrite oxidising bacteria (NOB) and other heterotrophicorganisms (OHO). However, treatment with FNA results in a significantlygreater reduction in NOB and 0110, when compared to the reduction thatoccurs in AOB. During full nitrification, AOB oxidise ammonia tonitrite, NOB then oxidise nitrite (NO2-) to nitrate (NO3-). Theoxidation of nitrite to nitrate consumes 25% of the oxygen required forammonium oxidation to nitrate. In the subsequent denitrification,nitrate is reduced to nitrite, and nitrite is further reduced todinitrogen gas via nitric oxide and nitrous oxide. This process requiresorganic carbon as the electron donor. The amount of carbon required fornitrate reduction to nitrite represents 40% of that requires for fullconversion of nitrate to dinitrogen gas. By reducing AOB to a certainextent and reducing AOB and OHO to a greater extent by treatment withFNA, the amount of nitrite oxidized to nitrate is reduced, therebyreducing the amount of oxygen required for the oxidation of ammonium,and the amount of carbon required to support the reduction steps. Thesavings in oxygen and carbon consumption can be up to 25% and 40%,respectively.

Accordingly, in a fourth aspect, the present invention provides a methodfor sludge treatment, the method comprising the steps of treating thesludge with free nitrous acid to reduce a level of AOB and to reduce NOBand OHO to a significantly greater level to thereby minimise oxidationof nitrite to nitrate, and subsequently subjecting nitrite produced to areduction treatment to produce dinitrogen gas. Desirably, the step oftreating the sludge with FNA largely eliminates NOB. OHO may also belargely reduced in that step, but will not be eliminated due to theirfaster growth rates compared to AOB and NOB.

In some embodiments, the present invention envisages treating the sludgewith other chemicals, as well as with free nitrous acid. The otherchemicals may be selected from hydrogen peroxide or oxygen. It will beunderstood that the present invention encompasses the inclusion of freenitrous acid with other chemical treatment agents that may be used inthe treatment of sludge.

In some embodiments, the method of the present invention may beconducted at ambient temperature or in the absence of external heating.In other embodiments, the method of the present invention may beconducted at elevated temperatures. For example, the method may beconducted with temperatures in the range of 30 to 60° C. The presentinvention encompasses operation of the method at any suitabletemperature.

The present invention also encompasses any suitable treatment time thatwill produce the desired results obtained by the present invention. Itis believed that treatment times in the order of from one hour to 1 weekare suitable, more suitably between six hours and two days. However, thepresent invention may also encompass significantly longer treatmenttimes. In some embodiments, the treatment time may be calculated as theaverage residence time for the sludge in the reactor or in the processvessel.

The solution containing free nitrous acid may be formed from a nitritecontaining solution generated in a water treatment processing plant. Inthis manner, formation of the solution containing free nitrous acid mayoccur at relatively low cost. Furthermore, in this embodiment, largequantities of solution containing free nitrous acid can be formed.Formation of the free nitrous acid stream can be achieved usingbiological processes. The nitrite containing solution may be generatedin accordance with the process as described in our international patentapplication number PCT/AU2011/000482, the entire contents of which areincorporated herein by cross reference.

In some embodiments, it may be desirable to thicken the sludge beforetreating the sludge in accordance with the present invention. Somewastewater treatment plants have a sludge thickener to obtain a moreconcentrated sludge for the sludge treatment. If this is the case, thetreatment step of the present invention may be placed after thethickener. Without wishing to be bound by theory, it is believed that bythickening the sludge, it will be possible to reduce the amount of freenitrous acid required (due to reduction in sludge volume and assumingthat it will not be necessary to increase the effective free nitrousacid concentration). This would reduce the cost for provision of thefree nitrous acid. Furthermore, it will also be possible to reduce theamount of free nitrous acid that is fed to the bioreactor for treatingwastewater or the anaerobic or an aerobic sludge digester followingtreatment of the sludge in accordance with the present invention. Inthis regard, feeding free nitrous acid to the bioreactor is expected tobe detrimental to operation in the bioreactor or the digester. In someembodiments, it may be desirable to slowly feed the treated sludge tothe bioreactor, which would tend to dilute the free nitrous acid,thereby reducing its toxic effects in the bioreactor. However, nitriteis an electron acceptor and it will oxidise some organic carbon producedduring the treatment step of the present invention. Therefore, it may bedesirable to add as little nitrite as possible per unit mass of sludge.In this regard, the treatment step of the present invention could becarried out at a lower pH, as less nitrite will be required to producethe desired level of free nitrous acid. Thickened sludge may also befavoured as this may allow a reduction in the nitrite/sludge mass ratio.

The liquid containing free nitrous acid may be generated as part of theoverall water treatment process. In one embodiment, the liquidcontaining free nitrous acid is generated by providing a nitritecontaining liquid having an acidic pH.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph of nitrate and, methanol consumption in batchexperiments performed prior to and after a 48 hour starvation period;

FIG. 2 shows graphs of batch tests measuring the activity recovery ofthe experimental sludge;

FIG. 3 shows the dependency of viable cell ratios on FNA concentrationafter exposure time of: A—8 h; B-24 h; C-48 h. ● viable cells beforeexposure; ∘ viable cells after exposure;

FIG. 4 shows the dependency of ammonium release rate and FNAconcentrations during the sludge treatment with FNA;

FIG. 5 shows the recovery of the nitrate reduction rate activity afterdifferent periods of sludge treatment with FNA: A—8 h; B-24 h; C-48 h.Different symbols represent the denitrification activity after differentrecovery times: ● 0 h recovery time; ∘ 24 h recovery time; ▾ 48 hrecovery time; Δ 72 h recovery time;

FIG. 6 shows nitrate reduction rate from the sludge used (●) and afterbeing exposed 48 h at certain pH (∘);

FIG. 7 shows nitrate concentration as a function of the duration ofaerobic digestion;

FIG. 8 shows Oxygen Uptake Rate (OUR) as a function of the duration ofaerobic digestion. In FIG. 8, the uppermost line shows the results foradded FNA-treated sludge, the lowest line at the right hand end of thelines in the graph relates to added untreated sludge and the other linerelates to untreated effluent; and

FIG. 9 shows activities of AOB and NOB, relative to the activities priorto FNA treatment (error bars indicate the standard errors). AOB:ammonia-oxidising bacteria; NOB: nitrite-oxidising bacteria; OHO:ordinary heterotrophic bacteria.

EXAMPLE 1

This example demonstrates the biocidal effect of FNA on denitrifyingbiomass.

In order to determine the effect of contacting a sludge with a liquidcontaining free nitrous acid, a sludge from a denitrifying sequencingbatch reactor was grown using a synthetic feed containing methanol andnitrate. Methanol provided the carbon source and nitrate provided theelectron acceptor. The following procedure was followed:

1. Sludge removed from the denitrifying SBR (sequencing batch reactor).The biomass was enriched for 5 months in an 8 L reactor with methanol asthe carbon source and nitrate as the electron acceptor.

2. A batch experiment was performed at pH 6 for initial biomass activitydetermination. At the beginning of the test, nitrate and methanol wereadded. Liquid phase samples were taken every 15 minutes for the analysisof nitrate and methanol. The consumption rates of methanol and nitratewere determined. All other batch tests described below were alsoconducted at pH 6.3. Fresh sludge of 2 L was removed from the SBR at the end of a cycle,and equally divided into two batch reactors, namely the control and theexperimental reactors.

-   -   a. The sludge in the control reactor was kept at pH 6 under        mixed conditions for 48 hours;    -   b. The sludge in the experimental reactor was kept at pH 6 under        mixed conditions for 48 hours. Nitrite was added to the reactor        at the beginning of the test, which resulted in 500 mg NO2″-N/L        in the reactor. The concentration of free nitrous acid was        estimated to be approximately 0.97 ppm.        4. 24 hours after the above conditions were started, sludge        samples of 250 mL each were removed from both the control and        the experimental reactors, and batch experiments as described in        Step 2 were performed. Before the addition of nitrate and        methanol, the sludges were washed with effluent from the parent        SBR to ensure that both sludge samples were nitrite-free.        5. The above tests were repeated at 48 hours.        6. Sludge samples were also removed at 48 hours from both        reactors to quantify the live/dead cells using the Live/Dead        BacLight Bacterial Viability assay.        7. At 48 hours, the experimental reactor was washed with the        effluent from the parent SBR to remove the residual nitrite.        Nitrate and methanol were then added to the reactor resulting in        concentrations of 50 mgNO2⁻-N/L and 150 mg/L, respectively. The        methanol and nitrate consumptions rates at the end of Day 3, Day        4 and Day 7 were measured through measuring the nitrate and        methanol concentrations over a period over one hour each time.        This series of tests were carried out to monitor the recovery of        the biomass activity after being exposed to FNA for 48 hours.        Experiments with Full-Scale Sludge

Similar tests were performed on a full-scale sludge. However, noactivity tests were carried out. The experiments focused on verifyingthe biocidal effect of FNA on bacteria in a full-scale sludge taken fromlocal sewage treatment plant treating primarily domestic wastewater. Thenitrite concentration applied to the experimental reactor was 500mgNO2-N/L. pH was maintained at 6.0 in both the control and experimentalreactors.

Results

Treatment of the Methanol Sludge

Table 1 shows the activity of the sludges in the control andexperimental reactors. FIG. 1 shows detailed batch test results on Day 0and Day 2. Table 2 shows the percentages of live and dead cells in bothreactors 48 hours after the starvation.

TABLE 1 Summary of the methanol and nitrate consumption rates during the48 hour starvation period. Day 1 Day 2 Control Experimental ControlExperimental Day 0 reactor reactor reactor reactor mg N—NO₃ ⁻/ 0.5240.135 0.014 0.54 0.004 gVSS*min mg Methanol/ 1.270 0.330 0.051 1.61 0.0gVSS*min

TABLE 2 Live and dead cells in the control and experimental reactors 48hours after the starvation. Experimental (16 images) Control (21 images)Average Average (% dead cells) St dev. St. Error (%) St dev. St. Error40.4 12 3.2 7.06 3.6 0.79Recovery of the FNA Treated Methanol Sludge

Table 3 shows the activity recovery of the biomass in the experimentalreactor. The detailed experimental results are shown in FIG. 2.

TABLE 3 Activity recovery of the biomass in the experimental reactor(Day 2 is the time when recovery started) Day 2 Day 3 Day 4 Day 7 mgN—NO₃ ⁻/ 0.004 0.004 0.022 0.089 gVSS*min mg Methanol/ 0 0.133 0.0670.235 gVSS*minTreatment of the Full-Scale Sludge

TABLE 4 Live and dead cells in the control and experimental reactors 48hours after the starvation (Full- scale sludge) FNA TREATED (29 images)Control (28 images) Average Average (% dead cells) St dev. St. Error (%)St dev. St. Error 63.6 14.9 0.13 17.6 5.6 0.08

The above experiments showed that free nitrous acid (FNA) is stronglybiocidal. Exposed to FNA at a concentration of approximately 1 ppm for48 hours, a substantial fraction of the bacteria in the sludge werekilled. The biomass lost 99% of its activity.

This recovery of the activity was slow, which was likely due to thegrowth of the residual live cells rather than the recovery of deadcells.

As the FNA killed a large percentage of the bacteria in the sludge,those bacteria would be more easily biodegradable and therefore theircarbon content would be more readily available for utilisation by themicrobial population in an anaerobic or an aerobic digester or in abioreactor for treating wastewater. Thus, enhanced utilisation of thesludge in the digester or in the bioreactor is possible. This would alsolead to reduction of the amount of sludge to be disposed of.

Accordingly, as a further advantage, embodiments of the presentinvention can also reduce the amount of sludge that needs disposal. Thisalso adds to the benefits and economics of the present invention.

The FNA can be generated as part of the overall water treatment process,thereby allowing the FNA to be formed at a low price. Accordingly, thepresent invention becomes economically favourable.

EXAMPLE 2

The aim of this study is to experimentally evaluate the feasibility ofFNA to improve the biodegradability of secondary sludge. In general,primary sludge is readily hydrolysable (Mahmood and Elliott, 2006;Foladori et al., 2010). Hence, this study only focussed on secondarysludge. A series of batch tests were conducted through the use of anenriched methonal-utilising denitrifiers culture, which was employed assecondary sludge in this study. LIVE/DEAD staining was performed toexamine the biocidal effect of FNA by verifying the integrity of cellmembrane. The deactivation of secondary sludge and the recovery of theiractivities after FNA treatment were investigated by comparing thenitrate reduction rates of the experimental and control reactors. Theimprovement of biodegradability of secondary sludge was assessed by themeasurement of oxygen uptake rates (OURs) and nitrate accumulation.

Materials and Methods

LIVE/DEAD staining

The LIVE/DEAD BacLight™ bacterial viability kits (Moleculer ProbesOL-7012) were used to discriminate between viable cells and dead cells(Ziglio et al., 2002; Invitrogen Molecular Probes, 2003). The BacLight™bacterial viability kits contain green-fluorescent nucleic acid stainSYTO® 9 and red-fluorescent nucleic acid stain Propidium Iodide (PI).When used alone, the SYTO® 9 stain generally labels all bacteria thathave both intact membranes and damaged membranes. In contrast, PI stainpenetrates only those bacteria with damaged membranes, causing areduction in the SYTO® 9 stain fluorescence when both dyes are present.For this reason, bacteria with intact cell membranes (viable cells)stain green fluorescence, whereas bacteria with damaged membranes (deadcells) stain red fluorescence.

During the staining experiments, sludge samples (1 ml in each testing)were transferred into 5-ml plastic tubes in conjunction with 1.5 μl ofSYTO® 9 and 1.5 μl of PI, and incubated in a dark place for 15 min atthe room temperature, making staining reactions complete. Then, slideswith stained sludge samples (10 μl on each slide) were observed andphotographed using a confocal laser scanning microscope (Zeiss LSM 510META), equipped with a Krypton-Argon laser (488 nm) and two He—Ne lasers(543 and 643 nm).

Thirty images were taken randomly for each sample. Quantification ofviable and dead cells was performed with Daime version 1.3.1 using thebiovolume fraction function (Daims et al., 2006). Based on the obtainedvalues, ratio of green fluorescence to total fluorescence (red+greenfluorescence) was thus determined, which are equivalent to ratio ofviable cells to total cells (viable+dead cells).

Results

Biocidal Effect of FNA on Secondary Sludge

FIG. 3 shows the dependency of viable cell ratios on FNA concentrationafter the specified exposure times. The results presented in FIG. 4 showthat:

Fraction of viable cells decreased with increasing FNA concentration.

Time of exposure to FNA also affects cell viability. Smaller live cellfraction is observed with 48 h of exposure, with the biggest differenceobserved at the highest FNA concentrations tested.

Ammonia Release During FNA Treatment.

FIG. 4 shows the dependency of ammonium release rate and FNAconcentrations during the sludge treatment with FNA. The results in FIG.4 show that:

NH4+ release rate under famine conditions is an indication of thehydrolysis of intracellular compounds release during the decay of dyingcells. This hydrolysis is taken place by the activity of other livingmicroorganisms present in the sludge.

A decrease on the NH4+ release rate while increasing the FNAconcentration where the sludge is being exposed to could indicate thereis less biological activity to carry out this hydrolysis and thereforeNH4+ is not being produced.

Activity of Secondary Sludge after FNA Treatment

FIG. 5 shows the recovery of the nitrate reduction rate activity afterdifferent periods of sludge treatment with FNA. The results shown inFIG. 5 demonstrate that:

Sludge exposure time to FNA has an effect on the level of biologicalactivity remaining (measured as denitrification activity since thesludge was mainly composed by denitrifying microorganisms).

With a lower exposure time (8 h to FNA, FIG. 3.A), biomass activitydisplays a recovery, while when exposed to the longest time to FNA, thebiomass activity recovery is almost negligible even at the lowest FNAconcentration exposure.

FIG. 6 shows nitrate reduction rate from the sludge used (●) and afterbeing exposed 48 h at certain pH (∘). The results of FIG. 6 show that pHhas also a detrimental effect on activity recovery. This negative effectincreases when lowering the pH and increasing the exposure time.

Aerobic Biodegradability of the FNA Treated Sludge

3 batch reactors were inoculated with full-scale WWTP fresh sludge,previously aerated to deplete any COD present in the sludge. These batchreactors were run identically, with the pH controlled at 7 and the DOkept between 3-4 ppm. In the 1st reactor, 100 mL of FNA treated sludge(2.02 mg N—HNO2/L during 48 h) was added. In the second reactor, 100 mLof untreated sludge was added. In the 3rd reactor, treated effluent(non-detectable COD, no detectable N) from a lab-scale denitrifyingreactor was added. In the 2nd and 3rd reactor, nitrite was added tomimic the concentration of nitrite present in the 1st reactor after theaddition of the FNA treated sludge (45 mg N—NO2-/L). FIG. 8 showsnitrate concentration as a function of the duration of aerobicdigestion.

The results of FIG. 7 demonstrate that a higher increase of nitrate inthe 1st reactor where the FNA treated sludge has been added indicates amajor biodegradability of this sludge. The hypothesis behind thisaffirmation is that biomass present in the reactor can hydrolyse some ofthe intracellular compounds from those cells that are damaged or dead.The product of hydrolysis would be NH4+ but due to the presence ofnitrifiers, it is converted to nitrate.

Table 5 shows measured data for mass balance evaluation.

TABLE 5 Measured data for mass balance evaluation MLVSS (mg/L) NO₃ (mgN/L) Averaged OUR Reactor initial final initial final (mg O₂/L · h)Reactor with 3340 2660 4.25 106.4 8.096 · 55 FNA-treated sludge Reactorwith 3340 2840 5.95 94.3 6.614 · 50 untreated sludge Reactor with 30402515 5.81 92.7 6.404 · 63 effluent

The mass balance calculations show that:

The extra VSS consumption in Reactor 1 compared to Reactor 3 was about(3340−2660)−(3040−2515)=155 mg/L

The extra N released in Reactor 1 compared to Reactor 3 was about 15.3mgN/L. The NNSS release ratio was about 15.3/155=9.9%.

FIG. 8 shows the Oxygen Uptake Rate (OUR) as a function of the durationof aerobic digestion. This shows that OUR in reactor with FNA-treatedsludge (Reactor 1) was consistently higher than that in the two otherreactors (Reactors 2 and 3). This suggests that the sludgebiodegradability was improved after FNA treatment.

Mass Balance

The OUR in Reactor 1 was about 1.92 mg/L.h higher than the OUR inReactor 3 (Table 5). This is about 46 mgO2/L.day. Over the 5.79 dayperiod, the total extra O₂ consumption would be 266 mgO2/L. The extra Nreleased in Reactor 1 compared to Reactor 3 was about 15.3 mgN/L. 15.3mg N/L can consume 70 O2/L (15.3*4.57). The amount of the sludge addedwas 100 ml. The data suggest that the FNA-treated sludge provided 3920mgCOD/L ((266−70)*20) over the 5.79 day period (392 mgCOD/0.1 L).

FNA-treated concentrated sludge (SBR) VSS: 6120 mg/L. The VSSconsumption ratio in the FNA-treated sludge was about 155*20 (dilutiontime)/6120=50%.

The COD concentration of FNA-treated sludge was around 8017 mg COD/L.This indicates that FNA treated-sludge provided 400 mg COD/0.1 L(8017*0.1*50%; 50% means VSS consumption ratio in the FNA-treatedsludge) over the 5.79 day period, which was comparable to 392 mg COD/0.1L determined according to OUR. This implies that the results of OUR werereasonable.

EXAMPLE 3

This example had an objective of evaluating differential killings of AOB(ammonia oxidizing bacteria), NOB (nitrite oxidizing bacteria) and OHOs(ordinary heterotrophic organisms) by FNA.

Experiment Protocol (Briefly):

Step 1: Measuring the original activities of AOB, NOB and OHOs (i.e.,before FNA treatment):

Activities of AOB and NOB:

Sludge was taken out from the parent reactor (SBR) at the end of anaerobic period and then transferred into a batch reactor. Afterwards,ammonium and nitrite stock solutions were added to the batch reactor,resulting in the ammonium and nitrite concentrations of 25 mg NH4-N/Land 20 mg NO2-N/L, respectively. Air was supplied during the wholeexperiment period (DO was not limiting, i.e. >3 mg/L). pH was controlledin the range of 7.5-8 during the whole experimental period. Theactivities of AOB and NOB were determined as biomass-specificnitrite+nitrate and nitrate production rates, respectively.

Aerobic Activity of OHOs:

Sludge was taken out from the parent reactor at the end of an aerobicperiod and then transferred into a batch reactor. Afterwards, sodiumacetate and ammonium stock solutions were added to the batch reactor,resulting in the COD and ammonium concentrations of 150 mg COD/L and 20NH4-N/L, respectively. Air was supplied during the whole experimentperiod (DO was not limiting, i.e. >3 mg/L). pH was controlled in therange of 7.5-8 during the whole experimental period. The aerobicactivity of OHO was determined as biomass-specific COD consumptionrates.

Step 2: Exposing sludge to various FNA levels for 24 h

The experimental conditions applied in batch testing are set out inTable 6.

TABLE 6 Experimental conditions applied in batch tests in Example 3(exposure time = 24 h) Batch 1 Batch 2 Batch 3 Batch 4 Batch 5 Batch 6Control NO₂ ⁻ (mgN/L) 100 200 300 550 700 1100 0 pH 6 6 6 6 6 6 around7.5 FNA (mgN/L) 0.22 0.45 0.67 1.24 1.57 2.47 0Step 3: Measuring the Activities of AOB, NOB and OHOs Following FNATreatment and after 2-h Recovery, with the Procedures Described Above.The Results are Shown in FIG. 9.

The above differential killing can be utilized to achieve nitrogenremoval via the nitrite pathway, that is, though ammonium oxidation tonitrite and then nitrite reduction to dinitrogen gas (NH4+□NO2-□N2)without going through nitrate. This can be achieved throughappropriately chosen FNA level and treatment duration, and the solidsretention time in the SBR such that NOB are eliminated from the systemwhile AOB are maintained. This process reduces the oxygen requirementfor nitrification by 25% and the carbon requirement for denitrificationby 40%.

EXAMPLE 4

This example investigates pretreating a sludge in accordance with anembodiment of the present invention in order to demonstrate that thepresent invention can reduce the amount of sludge that would otherwisebe formed. In this experiment, a lab-scale sequencing batch reactor(SBR) with a working volume of 8 L was used in this study. The SBR wasoperated with a cycle time of 6-h, consisting of 10 min anoxic feed, 70min anoxic reaction, 225 min aerobic reaction, 5 min sludge wasting, 45min settling and 5 min decanting periods. In each cycle, 2 L ofsynthetic wastewater containing 400 mg COD and 50 mgN/L TKN including 40mgNH4+-N/L, made from milk powder and ammonium chloride, along withother trace elements, was pumped into the SBR in the 10 min feed period,resulting in a hydraulic retention time (HRT) of 24 h. Before settling,around 133 ml of mixed liquor was wasted, giving rise to a sludgeretention time of 15 days. The SBR was operated at a temperature of18±2° C., with DO being controlled between 1.5-2.0 mg/L by aprogrammable logic controller (PLC) in the aerobic period. The pH in thesystem was recorded but not controlled and fluctuated between 7.2 and7.5 during a typical cycle.

50% of the wasted mixed liquor was treated by 2.0 mg HNO2-N/L forapproximately 24 h, 30 h, 36 h and 42 h, respectively. Afterwards, thefree nitrous acid (FNA)-treated sludge was returned to the SBR andtherefore sludge retention time (SRT) was maintained at approximately 30days.

The sludge wasted from the SBR was allowed to settle. 50% of theconcentrated sludge was treated with free nitrous acid (FNA) atapproximately 2 ppm (pH=6.0) and for approximately 24 hours and thesludge was then recycled to the reactor. The other 50% of the sludge wassent to disposal.

A control SBR operating under identical conditions was also fed with thesame wastewater, but there was no recycle of any sludge to this reactor.

Table 7 shows the measured and predicted MLSS (mixed liquor suspendedsolids) and MLVSS (mixed liquor volatile suspended solids) data (withstandard errors) for this test after the reactors reached steady state.

TABLE 7 Measured and predicted MLSS and MLVSS data (with standarderrors) for sludge minimization test after reaching steady state MLSS(mg/L) MLVSS (mg/L) Predicted if Predicted if FNA did not FNA did notimprove sludge improve sludge Reactor Measured degradability Measureddegradability Control 1527 ± 6 — 1465 ± 6 — reactor (n = 26) (n = 26)FNA 1762 ± 9 2369 1686 ± 8 2274 reactor (n = 14) (n = 14)

The mass balance analysis of the MLSS and MLVSS indicate that:

a) approximately 75% of the FNA treated sludge was degraded in thereactor;

b) overall sludge production in the experimental SBR system representsonly 60% that from the control SBR. In other words, sludge production isreduced by 40%. The cost saving implication is substantial given thefact that sludge treatment and disposal represent up to 50-60% of thetotal costs in a wastewater treatment plant.

The concentrations of effluent NH4-N, NO2-N and NO3-N were also measuredand the results are shown in Table 8:

TABLE 8 Measured effluent NH₄—N, NO₄—N and NO₃—N data (with standarderrors) of the two reactors in steady state NH₄—N (mg/L) NO₂—N (mg/L)NO₃—N (mg/L) With FNA With FNA With FNA Control treatment Controltreatment Control treatment 0.1 ± 0.1 0.1 ± 0.01 0.01 ± 0 0.01 ± 0 13.8± 0.4 11.8 ± 0.4

The data in Table 8 show that the return of the FNA-treated sludge tothe experimental SBR reduced effluent nitrate concentration by 2 mgN/L(that is, by 15%).

Those skilled in the art will appreciate that the present invention maybe susceptible to variations and modifications other than thosespecifically described. It will be understood that the present inventionencompasses all such variations and modifications that fall within itsspirit and scope.

Throughout this specification, the term “comprising” and its grammaticalequivalents shall be taken to have an inclusive meaning unless thecontext of use indicates otherwise.

The invention claimed is:
 1. A method for treating a sludge, the methodcomprising: (a) contacting the sludge with free nitrous acid to obtain amixture thereof, wherein the mixture of sludge and free nitrous acid hasa pH that is less than 6, and wherein the mixture of sludge and freenitrous acid has a free nitrous acid content of at least 0.3 ppm, suchthat a substantially large part of bacteria is eliminated from thesystem upon contacting the sludge with the free nitrous acid; and (b)feeding the mixture of sludge and free nitrous acid from step (a) to abioreactor for treating wastewater, or an anaerobic or aerobic sludgedigester.
 2. A method as claimed in claim 1 wherein the sludge comprisesa sludge from a secondary settler or from a bioreactor treatingwastewater.
 3. A method as claimed in claim 1 wherein the mixture ofsludge and free nitrous acid has a pH that is than
 4. 4. A method asclaimed in claim 1 wherein the mixture of sludge and free nitrous acidhas a free nitrous acid content of at least 0.5 ppm.
 5. A method asclaimed in claim 1 wherein the free nitrous acid is continuously addedto the sludge being treated or the free nitrous acid is added to thesludge on an intermittent basis.
 6. A method as claimed in claim 1wherein the sludge is contacted with free nitrous acid by contacting thesludge with a liquid stream containing free nitrous acid.
 7. A method asclaimed in claim 6 wherein the liquid stream containing free nitrousacid has a pH that is less than
 4. 8. A method as claimed in claim 6wherein the liquid stream containing free nitrous acid has a freenitrous acid content of at least 0.5 ppm.
 9. A method as claimed inclaim 1 wherein the sludge is thickened prior to treatment.
 10. A methodas claimed in claim 1 wherein operating parameters are controlled suchthat nitrite oxidising bacteria are largely eliminated from the systemwhilst ammonium oxidising bacteria remained in the system, wherebynitrogen removal is achieved via the nitrite pathway.
 11. A method asclaimed in claim 1 wherein other treatment chemicals are also added. 12.A method as claimed in claim 11 wherein the other treatment chemicalsare selected from hydrogen peroxide and oxygen.
 13. A method as claimedin claim 1 wherein a treatment time from one hour to 1 week is utilised.14. A method for treating a sludge comprising treating the sludge inaccordance with a method as claimed in claim 1 and passing the treatedsludge to a digester or to a bioreactor for treating wastewater.
 15. Amethod for treating a sludge, the method comprising the steps of: (a)treating the sludge with free nitrous acid to form a mixture thereof andreduce a level of ammonium oxidizing bacteria (AOB) and to reducenitrate-oxidizing bacteria (NOB) and other heterotrophic organisms (OHO)to a significantly greater level to thereby minimise oxidation ofnitrite to nitrate, wherein the mixture of sludge and free nitrous acidhas a pH that is less than 6, and wherein the mixture of sludge and freenitrous acid has a free nitrous acid content of at least 0.3 ppm; and(b) subsequently subjecting the nitrite produced in step (a) to areduction treatment to produce dinitrogen gas.
 16. A method as claimedin claim 15 wherein the step of treating the sludge or other effluentwith FNA largely eliminates NOB.
 17. A method as claimed in claim 15wherein the step of treating the sludge or other effluent with FNAlargely reduces OHO.
 18. A method as claimed in claim 1 wherein themixture of sludge and free nitrous acid has a pH that is less than 2.19. A method as claimed in claim 6 wherein the mixture of sludge andfree nitrous acid has a pH that is less than
 2. 20. A method as claimedin claim 1 wherein the mixture of sludge and free nitrous acid has afree nitrous acid content of at least 1 ppm.
 21. A method as claimed inclaim 1 wherein the mixture of sludge and free nitrous acid has a freenitrous acid content of at least 2 ppm.
 22. A method as claimed in claim6 wherein the liquid stream containing free nitrous acid has a freenitrous acid content of at least 1 ppm.
 23. A method as claimed in claim6 wherein the liquid stream containing free nitrous acid has a freenitrous acid content of at least 2 ppm.